Directed Rh(I)-Catalyzed Asymmetric Hydroboration of Prochiral 1-Arylcycloprop-2-ene-1-carboxylic Acid Derivatives

This is the peer reviewed version of the following article: A. Edwards, M. Rubina, M. Rubin, Chem. Eur. J. 2018, 24, 1394., which has been published in final form at http://doi.org/10.1002/chem.201704443. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.A full account on rhodium-catalyzed asymmetric, directed hydroboration of functionalized prochiral cyclopropenes affording enantiomerically enriched cyclopropylboronates is reported. The scope and limitations of two alternate directing groups, ester and carboxamide, are evaluated. It was found that hydroboration of esters appeared to be more sensitive to substitution in the aromatic ring of the substrates. Specifically, ortho-halogens were detrimental for diastereo- and enantioselectivity, possibly because of additional coordination with rhodium. In contrast, more Lewis-basic amide directing groups allowed for stronger chelation to the transition metal, leading to consistently high diastereo- and enantioselectivity in hydroboration across a broader range of substrates

Precursors of Cytochrome Oxidase in Cytochrome-Oxidase-Deficient Cells of Neurospora crassa

Three different cell types of Neurospora crassa deficient in cytochrome oxidase were studied: the nuclear mutant cni-1, the cytoplasmic mutant mi-1 and copper-depleted wild-type cells. * 1. The enzyme-deficient cells have retained a functioning mitochondrial protein synthesis. It accounted for 12–16% of the total protein synthesis of the cell. However, the analysis of mitochondrial translation products by gel electrophoresis revealed that different amounts of individual membrane proteins were synthesized. Especially mutant cni-1 produced large amounts of a small molecular weight translation product, which is barely detectable in wild-type. * 2. Mitochondrial preparations of cytochrome-oxidase-deficient cells were examined for precursors of cytochrome oxidase. The presence of polypeptide components of cytochrome oxidase in the mitochondria was established with specific antibodies. On the other hand, no significant amounts of heme a could be extracted. * 3. Radioactively labelled components of cytochrome oxidase were isolated by immunoprecipitation and analysed by gel electrophoresis. All three cell types contained the enzyme components 4–7, which are translated on cytoplasmic ribosomes. The mitochondrially synthesized components 1–3 were present in mi-1 mutant and in copper-depleted wild-type cells. In contrast, components 2 and 3 were not detectable in the nuclear mutant cni-1. Both relative and absolute amounts of these polypeptides in the enzyme-deficient cells were quite different from those in wild-type cells. * 4. The components of cytochrome oxidase found in the enzyme-deficient cells were tightly associated with the mitochondrial membranes. * 5. Processes, which affect and may control the production of enzyme precursors or their assembly to a functional cytochrome oxidase are discussed

Mass Density Profiles of LSB Galaxies

We derive the mass density profiles of dark matter halos that are implied by high spatial resolution rotation curves of low surface brightness galaxies. We find that at small radii, the mass density distribution is dominated by a nearly constant density core with a core radius of a few kpc. For rho(r) ~ r^a, the distribution of inner slopes a is strongly peaked around a = -0.2. This is significantly shallower than the cuspy a < -1 halos found in CDM simulations. While the observed distribution of alpha does have a tail towards such extreme values, the derived value of alpha is found to depend on the spatial resolution of the rotation curves: a ~ -1 is found only for the least well resolved galaxies. Even for these galaxies, our data are also consistent with constant density cores (a = 0) of modest (~ 1 kpc) core radius, which can give the illusion of steep cusps when insufficiently resolved. Consequently, there is no clear evidence for a cuspy halo in any of the low surface brightness galaxies observed.Comment: To be published in ApJ Letters. 6 pages. Uses aastex and emulateapj5.sty Typo in Eq 1 fixe

Clinical decision support system for point of care use--ontology-driven design and software implementation

OBJECTIVES: The objective of this research was to design a clinical decision support system (CDSS) that supports heterogeneous clinical decision problems and runs on multiple computing platforms. Meeting this objective required a novel design to create an extendable and easy to maintain clinical CDSS for point of care support. The proposed solution was evaluated in a proof of concept implementation. METHODS: Based on our earlier research with the design of a mobile CDSS for emergency triage we used ontology-driven design to represent essential components of a CDSS. Models of clinical decision problems were derived from the ontology and they were processed into executable applications during runtime. This allowed scaling applications' functionality to the capabilities of computing platforms. A prototype of the system was implemented using the extended client-server architecture and Web services to distribute the functions of the system and to make it operational in limited connectivity conditions. RESULTS: The proposed design provided a common framework that facilitated development of diversified clinical applications running seamlessly on a variety of computing platforms. It was prototyped for two clinical decision problems and settings (triage of acute pain in the emergency department and postoperative management of radical prostatectomy on the hospital ward) and implemented on two computing platforms--desktop and handheld computers. CONCLUSIONS: The requirement of the CDSS heterogeneity was satisfied with ontology-driven design. Processing of application models described with the help of ontological models allowed having a complex system running on multiple computing platforms with different capabilities. Finally, separation of models and runtime components contributed to improved extensibility and maintainability of the system

Cascade Birth of Universes in Multidimensional Spaces

The formation mechanism of universes with distinctly different properties is considered within the framework of pure gravity in a space of D > 4 dimensions. The emergence of the Planck scale and its relationship to the inflaton mass are discussed.Comment: 10 p., minor correction

The Isomorphism Relation Between Tree-Automatic Structures

An $\omega$-tree-automatic structure is a relational structure whose domain and relations are accepted by Muller or Rabin tree automata. We investigate in this paper the isomorphism problem for $\omega$-tree-automatic structures. We prove first that the isomorphism relation for $\omega$-tree-automatic boolean algebras (respectively, partial orders, rings, commutative rings, non commutative rings, non commutative groups, nilpotent groups of class n >1) is not determined by the axiomatic system ZFC. Then we prove that the isomorphism problem for $\omega$-tree-automatic boolean algebras (respectively, partial orders, rings, commutative rings, non commutative rings, non commutative groups, nilpotent groups of class n >1) is neither a $\Sigma_2^1$-set nor a $\Pi_2^1$-set

Possible Signature of Low Scale Gravity in Ultra High Enegry Cosmic Rays

We show that the existence of low scale gravity at TeV scale could lead to a direct production of photons with energies above 10^22 eV due to annihilation of ultra high energy neutrinos on relic massive neutrinos of the galactic halo. Air showers initialized in the terrestrial atmosphere by these ultra energetic photons could be collected in near future by the new generation of cosmic ray experiments.Comment: 5 pages, 3 figure

Measurement and Compensation of Horizontal Crabbing at the Cornell Electron Storage Ring Test Accelerator

In storage rings, horizontal dispersion in the rf cavities introduces horizontal-longitudinal (xz) coupling, contributing to beam tilt in the xz plane. This coupling can be characterized by a "crabbing" dispersion term {\zeta}a that appears in the normal mode decomposition of the 1-turn transfer matrix. {\zeta}a is proportional to the rf cavity voltage and the horizontal dispersion in the cavity. We report experiments at the Cornell Electron Storage Ring Test Accelerator (CesrTA) where xz coupling was explored using three lattices with distinct crabbing properties. We characterize the xz coupling for each case by measuring the horizontal projection of the beam with a beam size monitor. The three lattice configurations correspond to a) 16 mrad xz tilt at the beam size monitor source point, b) compensation of the {\zeta}a introduced by one of two pairs of RF cavities with the second, and c) zero dispersion in RF cavities, eliminating {\zeta}a entirely. Additionally, intrabeam scattering (IBS) is evident in our measurements of beam size vs. rf voltage.Comment: 5 figures, 10 page